CN114315704A - Bipyridine compound and synthesis method and application thereof - Google Patents
Bipyridine compound and synthesis method and application thereof Download PDFInfo
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- CN114315704A CN114315704A CN202111452671.8A CN202111452671A CN114315704A CN 114315704 A CN114315704 A CN 114315704A CN 202111452671 A CN202111452671 A CN 202111452671A CN 114315704 A CN114315704 A CN 114315704A
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- -1 Bipyridine compound Chemical class 0.000 title claims abstract description 45
- 238000001308 synthesis method Methods 0.000 title abstract description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical class N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims 1
- 238000001953 recrystallisation Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 27
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 21
- 239000010439 graphite Substances 0.000 description 20
- 229910002804 graphite Inorganic materials 0.000 description 20
- 239000010453 quartz Substances 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 239000000276 potassium ferrocyanide Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical class [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 9
- 239000001103 potassium chloride Substances 0.000 description 8
- 235000011164 potassium chloride Nutrition 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- RQFUZUMFPRMVDX-UHFFFAOYSA-N 3-Bromo-1-propanol Chemical compound OCCCBr RQFUZUMFPRMVDX-UHFFFAOYSA-N 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 2
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 2
- WSTOEGIEWBZMLU-UHFFFAOYSA-N 2-methyl-4-(2-methylpyridin-4-yl)pyridine Chemical compound C1=NC(C)=CC(C=2C=C(C)N=CC=2)=C1 WSTOEGIEWBZMLU-UHFFFAOYSA-N 0.000 description 2
- FULVBVMFFGNQTB-UHFFFAOYSA-N 4-(2,6-dimethoxypyridin-4-yl)-2,6-dimethoxypyridine Chemical compound COc1cc(cc(OC)n1)-c1cc(OC)nc(OC)c1 FULVBVMFFGNQTB-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 229940107816 ammonium iodide Drugs 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- ZTGQZSKPSJUEBU-UHFFFAOYSA-N 3-bromopropan-1-amine Chemical compound NCCCBr ZTGQZSKPSJUEBU-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PEIKTSJIUKYDPC-UHFFFAOYSA-N Diethyl 3-Bromopropylphosphonate Chemical compound CCOP(=O)(OCC)CCCBr PEIKTSJIUKYDPC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Fuel Cell (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention provides a bipyridine compound and a synthesis method and application thereof, wherein main constituent elements of the bipyridine compound are carbon, hydrogen, oxygen and nitrogen, the source of the bipyridine compound is wide and easy to obtain, and the bipyridine compound is far lower than that of a currently popular all-vanadium redox flow battery in production and utilization of large-scale redox flow batteries. Compared with the traditional bipyridine compounds, functional groups are introduced into the bipyridine compounds at four positions of 2,2,6 and 6, so that the molecular conjugate region is enlarged, the molecular stability is improved, and the service life of the battery is prolonged.
Description
Technical Field
The invention belongs to the technical field of large-scale energy storage, and particularly relates to a bipyridine compound and a synthetic method and application thereof.
Background
With the rapid development of human society, the problems of environmental pollution and energy shortage caused by fossil energy are increasingly aggravated, and the demand of human beings on renewable energy sources such as wind energy, solar energy and the like is increasingly urgent. However, the renewable energy has the characteristics of discontinuity, instability and the like, so that the grid connection is difficult and the utilization rate is low. Therefore, it is necessary to develop a high-efficiency, safe and low-cost energy storage technology.
Among a plurality of chemical energy storage technologies, the flow battery has the advantages of independent energy and power control, high safety performance, long service life, low cost and the like, and is particularly suitable for large-scale energy storage. In the existing flow battery technology, the main commercial application grades are all-vanadium flow batteries and zinc-bromine flow batteries, and the defects that the price of vanadium metal raw materials is continuously increased, the manufacturing cost of the batteries is increased, and the bromine is highly toxic and highly corrosive are overcome, so that the large-scale application of the flow batteries is limited. The water-based organic flow battery adopts water as a solvent and organic molecules soluble in water as active substances. The organic molecules are composed of C, H, O, N and other elements, have the advantages of low cost, rich resources, green safety and the like, and attract wide attention at home and abroad. In recent years, anthraquinone, TEMPO, oxazine and ferrocene active substances are reported to be used in familiar water-based organic flow batteries and show good electrochemical performance.
However, the current aqueous organic flow battery still faces some challenges, such as low solubility of active materials (organic matters), cross contamination of electrolyte through a diaphragm, low oxidation-reduction potential of positive electrode materials, high oxidation-reduction potential of negative electrode materials, and the like. Therefore, the development of a new organic molecule as an active material, which overcomes the above disadvantages, is of great significance for the development and application of aqueous organic flow batteries.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a bipyridine compound, a synthesis method and application thereof so as to solve the problem of low stability of the active material of the existing flow battery in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a bipyridine compound having the structural formula:
wherein, the substituent R1，R2，R3，R4All are Me, OMe, OEt, COOH and COONH4Any one of the above; r5And R6Are all OH, Me, OMe, N (Me)3、SO3 -COOH and PO3 2-Any one of the above; the value range of n is 1-16.
The invention is further improved in that:
preferably, the molecule of the bipyridine compound has a symmetrical or asymmetrical structure.
A process for synthesizing bipyridine compound from bipyridine and X1-(CH2)n-R is according to 1: (1-15) putting the mixture into a reactor according to the equivalent ratio, mixing a solvent in the reactor, heating and refluxing the mixture to react to obtain a product, and synthesizing a bipyridine compound;
X1-(CH2)nin-R, X1Is one of Cl, Br and I, R is OH, Me, OMe, N (Me)3、SO3 -COOH and PO3 2-N ranges from 1 to 16.
Preferably, X is1-(CH2)nR is one of 3-bromo-1-propanol or 2-bromoethanol.
Preferably, the solvent is one of acetonitrile, toluene, tetrahydrofuran or N, N dimethylformamide.
Preferably, the microwave heating power is 50-100W, and the heating time is 3-10 min.
Preferably, after the heating reflux reaction, the reaction product is sequentially filtered, washed, recrystallized and dried to obtain the product.
Use of the bipyridine-based compound described above as a negative electrode active material in an aqueous organic redox flow battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a bipyridine compound, which has the main constituent elements of carbon, hydrogen, oxygen and nitrogen, is wide and easily available in source, and has the cost far lower than that of a currently popular all-vanadium redox flow battery in the production and utilization of large-scale redox flow batteries. Compared with the traditional bipyridine compounds, the bipyridine compound of the invention introduces functional groups at four positions of 2,2,6 and 6 of bipyridine, enlarges the molecular conjugate region, regulates and controls the distribution of electron clouds on a pyridine ring, and the electron enrichment and electronegativity on the pyridine ring enhance the coulombic repulsion between molecules, effectively inhibits the dimerization phenomenon between molecules, and improves the molecular stability; the introduced functional group has large steric hindrance, and forms hydrogen bond acting force with nitrogen atoms in the leading position of the functional group, thereby forming protective action on nitrogen oxide reduction active sites, having repulsive action on OH-in water, inhibiting the attack of OH-in aqueous solution on the nitrogen active sites and improving the stability of molecules; the hydrogen bond acting force of molecules and water molecules is improved, the solubility of the molecules in water is increased, and the battery capacity is further improved.
The invention also provides a synthetic method of the bipyridine compound, which is simple, high in synthetic speed, low in cost and high in product yield. The compound is used as the cathode of the aqueous organic redox flow battery, and the aqueous organic redox flow battery with high energy density can be obtained by utilizing the characteristics of reversible redox reaction, good electrochemical reversibility, good stability and the like of the bipyridine compound.
The invention also discloses an application of the bipyridine compound, and the bipyridine compound has good electrochemical performance; the bipyridyl water system organic flow battery has the advantages of flexible power energy design, low cost and large-scale assembly application, and is very suitable for large-scale energy storage application.
Drawings
FIG. 1 is a CV diagram of the solution in example 1 of the present invention.
Fig. 2 is a capacity-voltage curve of the battery mounted in example 1 of the present invention.
Fig. 3 is a graph of the number of turns-coulombic efficiency-energy efficiency-discharge capacity of the battery mounted in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
in the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention; the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; furthermore, unless expressly stated or limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly and encompass, for example, both fixed and removable connections; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The invention discloses a bipyridine compound, which has a chemical reaction formula as follows:
wherein, the substituents R, R1，R2，R3，R4All are Me, OMe, OEt, COOH and COONH4Any one of the above; r5，R6Are all OH, Me, OMe, N (Me)3SO3 -、COOH、PO3 2-Thus, the molecule of the bipyridine compound is symmetricalOr an asymmetric structure. n represents the length of an alkyl chain, and the value range of n is 1-16. X1Is one of Cl, Br and I.
As one of the preferred embodiments, X1-(CH2)nR can be one of 3-bromo-1-propanol or 2-bromoethanol.
The specific process of the reaction is to mix bipyridine and X1-(CH2)nAnd (2) putting the-R into a reactor according to an equivalent ratio of 1 (1-15), heating for 2-10 min under the power of 50-100W, and filtering, washing, recrystallizing and drying after the reaction is finished to obtain the product.
The reaction solvent is one of acetonitrile, toluene, tetrahydrofuran and N, N-dimethylformamide.
The bipyridine molecule can be obtained by performing limited steps of addition and oxidation reaction on simple molecules of pyridine.
The bipyridine compound prepared by the invention can be applied to an aqueous organic redox flow battery, and the specific process is that organic molecules containing the bipyridine compound are used as a negative electrode active material; one or more of potassium ferrocyanide, TEMPO derivatives, ferrocene derivatives, iodine, sodium iodide, potassium iodide, ammonium iodide, bromine, potassium bromide, sodium bromide and ammonium bromide are mixed to be used as a positive electrode active substance; one or more of alkaline aqueous solution or neutral aqueous solution of salt is mixed to be used as electrolyte; taking a perfluorinated sulfonic acid-polytetrafluoroethylene copolymer membrane as an ion exchange membrane; two copper plates are used as current collectors of the battery; graphite plates with flow channels are used as flow field plates of a positive electrode and a negative electrode, and high-temperature oxidation or dilute acid carbon paper or graphite felt is used as an electrode of the battery. The assembling sequence of the battery is sequentially a copper current collector, a graphite plate flow channel, a carbon paper/graphite felt electrode, a perfluorinated sulfonic acid-polytetrafluoroethylene copolymer film, a carbon paper/graphite felt electrode, a graphite plate flow channel and a copper current collector.
Preferably, the neutral aqueous solution of the salt is one or more of sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sodium phosphate, potassium sulfate and sodium sulfate. More preferably, the neutral aqueous solution is a potassium chloride solution with the concentration of 0.1-2 mol/L
Preferably, the alkaline aqueous solution is prepared by dropwise adding a KOH aqueous solution into a neutral aqueous solution of salt, wherein the pH range is controlled to be 7-9, and the concentration is 1-6 mol/L.
Further, when the electrolyte is an alkaline aqueous solution, the positive electrode of the flow battery is a potassium ferrocyanide aqueous solution; when the electrolyte is a neutral aqueous solution of salt, the anode of the flow battery is one or a mixture of potassium ferrocyanide, TEMPO, ferrocene, iodine, sodium iodide, potassium iodide, ammonium iodide, bromine, potassium bromide, sodium bromide and an aqueous solution of ammonium bromide. The bipyridine compound has reversible oxidation-reduction reaction in the aqueous solution environment.
In an embodiment of the present invention, an assembling method of a bipyridine compound aqueous organic flow battery includes: bipyridine organic molecules are used as negative active substances; potassium ferrocyanide is used as a positive electrode active substance; KCl aqueous solution is used as electrolyte; the battery is sequentially assembled by a copper current collector, a graphite plate flow channel, a carbon paper/graphite felt electrode, a perfluorinated sulfonic acid-polytetrafluoroethylene copolymer film, a carbon paper/graphite felt electrode, a graphite plate flow channel and a copper current collector.
The following is set forth in connection with specific examples.
Example 1
1) Synthesis of bis (3-sulfopropyl) -2,2 ', 6,6 ' -tetramethyl-4, 4 ' -bipyridine
First, 2 ', 6,6 ' -tetramethoxy-4, 4 ' -bipyridine (1 equivalent) and 3-bromo-1-propanol (5 equivalents) were mixed in a tetrahydrofuran solution, added to a round-bottomed flask, stirred to completely dissolve all solids, and charged into a sealed quartz tube. The quartz tube was placed in a microwave oven and heated at 60W for 5min until the reaction mixture was cooled and filtered. Then washed 3 times with toluene solution and finally dried in vacuo to give a pink powder, named bis (3 hydroxy-propyl) -2,2 ', 6,6 ' -tetramethoxy-4, 4 ' -bipyridine in 75% yield.
2) Dissolving the product in 10mL of 1mol/L potassium chloride aqueous solution, stirring, and carrying out cyclic voltammetry on the prepared mixed solution by using a three-electrode system when the concentration of the mixed solution is 0.002mol/L, wherein silver/silver chloride is used as a reference electrode, a platinum electrode is used as a counter electrode, a glassy carbon electrode is used as a working electrode, and the sweep rate is 100mV/s, and the cyclic voltammetry scanning result is shown in figure 1.
From the data in fig. 1, the bipyridyl compound has a pair of significantly reversible redox peaks in a neutral aqueous solution, has good electrochemical reversibility, and has an average potential of-0.58V with a Standard Hydrogen Electrode (SHE) as a reference electrode, and shows a relatively negative redox potential as a negative electrode material.
3) Flow battery testing
Weighing the product of example 1, dissolving in 1mol/L potassium chloride aqueous solution, stirring to form a uniform solution, preparing into 0.1mol/L aqueous solution, taking 7mL as a negative electrode, weighing potassium ferrocyanide, dissolving in 1mol/L potassium chloride aqueous solution, stirring to form a uniform solution, preparing into 0.1mol/L potassium ferrocyanide solution, taking 10mL as a positive electrode. Putting a commercial graphite felt into a 1mol/L sulfuric acid solution, stirring and soaking for 10 hours, taking out, and washing with deionized water for later use. And assembling the batteries according to the sequence and the positions of the copper current collector, the graphite plate flow channel, the graphite felt, the ion exchange membrane, the graphite felt, the graphite plate flow channel and the copper current collector, and driving the liquid by using a peristaltic pump.
Performing performance test on the battery, performing constant current charging on the battery at a current of 200mA, keeping constant voltage charging after 1.2V, and stopping charging when the current is less than 5 mA; the battery is discharged with constant current at 200mA, and is kept discharged with constant voltage after 0.65V, and is cut off after the current is less than 5 mA. According to this system, a charge-discharge cycle test was carried out. The battery obtained from fig. 3 can work normally, and the coulombic efficiency of the battery is close to 100%, the energy efficiency is 87% and the discharge capacity of the battery is stable in the charge-discharge cycle test of over 1900 circles. Shows that the battery has stable circulation and long service life
Weighing the synthesized product, dissolving the synthesized product in 1mol/L potassium chloride aqueous solution, stirring to form uniform 0.5mol/L solution, taking 7mL as a negative electrode, weighing potassium ferrocyanide, dissolving the potassium ferrocyanide in 1mol/L potassium chloride aqueous solution, stirring to form uniform solution, preparing 0.25mol/L potassium ferrocyanide solution, and taking 20mL as a positive electrode. Putting a commercial graphite felt into a 1mol/L sulfuric acid solution, stirring and soaking for 10 hours, taking out, and washing with deionized water for later use. And assembling the batteries according to the sequence and the positions of the copper current collector, the graphite plate flow channel, the graphite felt, the ion exchange membrane, the graphite felt, the graphite plate flow channel and the copper current collector, and driving the liquid by using a peristaltic pump.
Example 2
2,2 ', 6,6 ' -tetramethoxy-4, 4 ' -bipyridine (1 equivalent) and 3-bromopropyl-3-methyl ammonium bromide (15 equivalents) were added to a round-bottomed flask, and an appropriate amount of N, N-dimethylformamide was added to dissolve completely. The mixed solution was charged into a sealed quartz tube. The quartz tube was placed in a microwave oven and heated at 100W power for 6min, after which the reaction mixture was cooled and filtered. Then washed 3 times with toluene solution and finally dried in vacuo to name bis (3-aminopropyl bromide) -2,2 ', 6,6 ' -tetramethoxy-4, 4 ' -bipyridine with a yield of 45%.
Assembling the product into a flow battery; the processes and parameters not specified in this example were the same as in example 1.
Example 3
2,2 ', 6,6 ' -tetramethoxy-4, 4 ' -bipyridine (1 equivalent) and diethyl-bromopropylphosphonate (10 equivalents) were mixed in anhydrous acetonitrile until all the solids were dissolved. Putting the mixed solution into a sealed quartz tube, placing the quartz tube in a microwave oven, heating for 3min under the power of 80W, cooling, filtering, washing the precipitate with acetonitrile, and vacuum drying to obtain white solid 1,1 '-bis (3- (diethoxyphosphoryl) propyl) - [2, 2', 6,6 '-tetramethoxy-4, 4' -bipyridine]Diammonium (1, 1' -dibromide (yield: 70%). This product (1 eq) was reacted with bromotrimethylsilane (10 eq) in dichloromethane N2And (4) mixing. The reaction mixture was stirred at room temperature overnight to give an orange solution. Then using excess anhydrous isopropanolQuenching gave an orange solution. The precipitate was filtered and dried in vacuo. The product was named 1,1 '-bis (3-phosphopropyl) -2, 2', 6,6 '-tetramethoxy-4, 4' -bipyridine with a yield of 90%.
Assembling the product into a flow battery; the processes and parameters not specified in this example were the same as in example 1.
Example 4
First, 2 ', 6,6 ' -tetramethoxy-4, 4 ' -bipyridine (1 equivalent), 3-bromo-1-methoxy (12 equivalents) and an appropriate amount of toluene were mixed until the solids were completely dissolved. Filling the mixed liquid into a sealed quartz tube, placing the quartz tube into a microwave oven, heating for 5min under the power of 50W, stopping for 30s, heating for 5min, cooling the reactant and filtering. Then washed 3 times with toluene solution and finally dried in vacuo to give a pink powder, named bis (3 methoxy-propyl) -2,2 ', 6,6 ' -tetramethoxy-4, 4 ' -bipyridine in 76% yield.
Assembling the product into a flow battery; the processes and parameters not specified in this example were the same as in example 1.
Example 5
First, 2 ', 6,6 ' -tetraethoxy-4, 4 ' -bipyridine (1 equivalent), 3-bromo-1-methoxy (10 equivalents) and an appropriate amount of tetrahydrofuran were mixed until the solid was completely dissolved. The mixed liquid was filled in a sealed quartz tube, the quartz tube was placed in a microwave oven, heated at 50W for 10min, and the reaction was cooled and filtered. Then washed 3 times with tetrahydrofuran solution and finally dried in vacuo to give a powder, named bis (3 hydroxy-propyl) -2,2 ', 6,6 ' -tetraethoxy-4, 4 ' -bipyridine, yield: 80%.
Assembling the product into a flow battery; the processes and parameters not specified in this example were the same as in example 1.
Example 6
First, 2 ', 6,6 ' -tetracarboxyl-4, 4 ' -bipyridine (1 eq), 3-bromo-1-propanol (10 eq) and an appropriate amount of N, N dimethylformamide were mixed until the solids were completely dissolved. Filling the mixed liquid into a sealed quartz tube, placing the quartz tube into a microwave oven, heating for 5min under the power of 100W, stopping for 30s, heating for 5min, cooling the reactant and filtering. Then washed 3 times with N, N dimethylformamide solution and finally dried in vacuo to give a powder, named bis (3 hydroxy-propyl) -2,2 ', 6,6 ' -tetracarboxy-4, 4 ' -bipyridine, yield: 70%.
Assembling the product into a flow battery; the processes and parameters not specified in this example were the same as in example 1.
Example 7
Dissolving the product (1 equivalent) in example 6 in water, dropwise adding ammonia water, monitoring the pH of the solution to 7-8 by using a pH test paper, stopping dropwise adding, stirring for 1h at room temperature, and removing the solvent by rotary evaporation to obtain solid powder, namely bis (3-hydroxy-propyl) -2,2 ', 6,6 ' -ammonium tetracarboxylate-4, 4 ' -bipyridine, wherein the yield is 100%.
Assembling the product into a flow battery; the processes and parameters not specified in this example were the same as in example 1.
Example 8
Mixing 2,2 ' -dicarboxy, 6,6 ' -dimethyl-4, 4 ' -bipyridine (1 equivalent), 3-bromo-1-propanol (1 equivalent) and an appropriate amount of acetonitrile until all are estimated to be dissolved, filling the mixed liquid into a sealed quartz tube, placing the quartz tube into a microwave oven, heating for 5min under the power of 60W, and cooling and filtering the reactant. Then washed 3 times with toluene solution and finally dried in vacuo to give a powder. Dissolving the powder in anhydrous N, N dimethylformamide solution, adding propyl sultone (2 equiv.), placing the mixed solution into a sealed quartz tube, placing the quartz tube into a microwave oven, heating for 3min under 100W, cooling the reactant and filtering. Then washed 3 times with N, N dimethylformamide solution and finally dried in vacuo to give a powder named 3-hydroxy-propyl-3-sulfonic acid-propyl-2, 2 ' -dicarboxy-, 6,6 ' -dimethyl-4, 4 ' -bipyridine with a yield of 60%.
Assembling the product into a flow battery; the processes and parameters not specified in this example were the same as in example 1.
Example 9
Dissolving the product (1 equivalent) in example 8 in water, dropwise adding ammonia water, monitoring the pH of the solution to 7-8 by using a pH test paper, stopping dropwise adding, stirring for 1h at room temperature, and removing the solvent by rotary evaporation to obtain solid powder, namely 3-hydroxy-propyl-3-sulfonic acid-propyl-2, 2 ' -ammonium dicarboxylate-, 6,6 ' -dimethyl-4, 4 ' -bipyridine, wherein the yield is 100%.
Example 10
First, 2 ', 6,6 ' -tetracarboxyl-4, 4 ' -bipyridine (1 equivalent), 3-bromo-1-butyric acid (10 equivalents) and an appropriate amount of N, N-dimethylformamide were mixed until the solids were completely dissolved. The mixed liquid was filled in a sealed quartz tube, the quartz tube was placed in a microwave oven, heated at 60W for 10min, and the reaction was cooled and filtered. Then washed 3 times with N, N dimethylformamide solution and finally dried in vacuo to give a powder, named bis (3 carboxy-propyl) -2,2 ', 6,6 ' -tetracarboxy-4, 4 ' -bipyridine, yield: 70%.
Assembling the product into a flow battery; the processes and parameters not specified in this example were the same as in example 1.
Example 11
The product (1 equivalent) in example 10 is dissolved in water, ammonia water is added dropwise, the dropwise addition is stopped after the pH of the solution is monitored to 7-8 by using a pH test paper, the solution is stirred for 1h at room temperature, the solvent is removed by rotary evaporation, and solid powder is obtained and named as bis (ammonium 3 carboxylate-propyl) -2,2 ', 6,6 ' -ammonium tetracarboxylate-4, 4 ' -bipyridine, and the yield is 100%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. A bipyridine compound, wherein the structural formula of the compound is:
wherein, the substituent R1，R2，R3，R4All are Me, OMe, OEt, COOH and COONH4Any one of the above; r5And R6Are all OH, Me, OMe, N (Me)3、SO3 -COOH and PO3 2-Any one of the above; the value range of n is 1-16.
2. A bipyridine compound according to claim 1, wherein the molecule of the bipyridine compound has a symmetrical or asymmetrical structure.
3. A synthetic method of bipyridine compounds is characterized in that bipyridine and X are mixed1-(CH2)nPutting the R into a reactor, mixing a solvent in the reactor, irradiating and heating by microwave to obtain a product, and synthesizing the bipyridine compound;
X1-(CH2)nin-R, X1Is one of Cl, Br and I, R is OH, Me, OMe, N (Me)3、SO3 -COOH and PO3 2-N ranges from 1 to 16.
4. The method for synthesizing a bipyridine compound according to claim 3, wherein the solvent is one of acetonitrile, toluene, tetrahydrofuran or N, N-dimethylformamide.
5. A method as claimed in claim 3, wherein the bipyridine compound is in the form of bipyridine and X1-(CH2)n-the equivalence ratio of R is 1: (1-15).
6. The method for synthesizing a bipyridine compound according to claim 3, wherein the microwave heating power is 50-100W, and the heating time is 3-10 min.
7. The method for synthesizing a bipyridine compound according to claim 3, wherein after the reaction of heating and refluxing, the reaction product is sequentially subjected to filtration, washing, recrystallization and drying to obtain the product.
8. Use of the bipyridine compound according to claim 1 as a negative electrode active material in an aqueous organic redox flow battery.
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